CN107522324A - Electrolytic manganese production Manganese in Waste Water recovery and waste water, the technique of waste gas integrated treatment - Google Patents
Electrolytic manganese production Manganese in Waste Water recovery and waste water, the technique of waste gas integrated treatment Download PDFInfo
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- CN107522324A CN107522324A CN201710995786.9A CN201710995786A CN107522324A CN 107522324 A CN107522324 A CN 107522324A CN 201710995786 A CN201710995786 A CN 201710995786A CN 107522324 A CN107522324 A CN 107522324A
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- waste water
- precipitation
- manganese
- hydroxide
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/206—Manganese or manganese compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of production Manganese in Waste Water recovery of electrolytic manganese and waste water, the technique of waste gas integrated treatment, first processing waste water containing chrome and polishing waste water, reducing agent is added in chromate waste water, by Cr6+It is reduced to Cr3+, hydroxide regulation pH is added, generates chromium hydroxide precipitation, slag is stacked into Special slag field after precipitation separates, and filtrate enters Mn-bearing waste water；Polish wastewater treatment；Manganese recycles；The techniques such as sulfate radical processing.The present invention is segmented in processing procedure, and chromate waste water and polishing waste water are handled respectively, first handle the waste water containing heavy metal ion, so as to reduce the content of beary metal in manganous carbonate slag, is advantageous to manganous carbonate slag recycling；Electrolytic manganese production process is mainly rinsing workshop section with water, wastewater treatment increase sulfate radical handling process, reduces SO4 2‑Content, sulfate radical is set to be down to 2g/L or so from original more than 10g/L, greatly reduce influence of the sulfate radical to manganese piece sulfur-bearing in electrolysis flushing water.
Description
Technical field
The present invention relates to electrolytic manganese production waste gas slag processing and recycle utilization technology field, be related to chromate waste water processing,
Wastewater treatment, manganese recycling are polished, manganese metal reclaims in particularly a kind of electrolytic manganese production waste water, caused by production process
The Environmental-protection comprehensive handling process that the processing of waste gas and water resource recycle.
Background technology
Issued according to State Environmental Protection Administration《Hunan, Chongqing, Guizhou San Sheng (city) border land's pollution by manganese renovation scheme》
With《Hunan, Chongqing, Guizhou San Sheng (city) border land's manganese industry pollution control supervisor's programme of work》, and the Guizhou Province environmental protection Room
Issue《Followed on requiring 9 undertaking treatment within a prescribed limit of time plant area of enterprise production waste water such as Song Tao Huifengs Meng Ye Co., Ltds and realizing
The notice that ring utilizes》, in April, 2011, company starts production waste water closed cycle demonstration project construction, while carries out at waste water
Science and engineering skill development test.
Company's electrolytic manganese production waste water mainly has Mn-bearing waste water, chromate waste water, polishes other waste water in waste water and workshop.Contain
Manganese waste water：Refer to waste water caused by cleaning minus plate, cleaning place, cleaning electrolytic cell etc., chromate waste water：The electrolytic manganese for just having gone out groove is lived
Property it is very high, be easily oxidized discoloration in atmosphere, it is necessary to carry out surface passivating treatment, to improve oxidation resistance, current electrolysis
The manganese production overwhelming majority is potassium bichromate using passivator, it is necessary to be cleaned after its passive metal manganese plate.Pole plate passivation is cleaned
Caused waste water, mainly contains Cr6+、Cr3+、Mn2+、SO4 2-Deng polishing waste water：After minus plate uses the long period, surface can become
Must be coarse, surface polishing need to be carried out, waste water caused by minus plate is rinsed after polishing, wherein mainly containing the heavy metals such as Fe, Ni, Cr
Ion.
In current electrolysis manganese cycling utilization of wastewater technique, most of wastewater source and reuse whereabouts are that potroom rinses
Manganese plate, only small part are used to washing cloth, clear groove etc., and the water for being used to rinse manganese plate must assure that pH as neutrality, and S contents in water
It is relatively low（SO4 2-Content is less than 2g/L）, otherwise can cause manganese plate appearance color exception and product sulfur-bearing raises.It is perennial through collecting
The number of production is it has been found that contain about 12 ~ 15g/L SO in waste water caused by potroom4 2-, waste water treatment process is not so far
Consider the processing of sulfate radical, still contain SO in the water after processing4 2- 10 ~ 12g/L, if being rinsed for manganese plate, manganese piece can be made
Sulfur-bearing rises 0.008% ~ 0.01%, reaches 30 ~ 40% to the influence for being electrolysed manganese product sulfur-bearing index.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided a kind of processing step is simple, processing
Cost is relatively low and can more meet to recycle desired waste water, waste gas treatment process, makes waste water, waste gas in electrolytic manganese production process
Mutually manganese metal recovery and water resource recycle in processing and waste water.
To solve above technical problem, the present invention carries out classification segment processing to electrolytic manganese production waste water, its wastewater treatment
Technique is, is first individually handled chromate waste water and polishing waste water, after carry out aggregation process again, it is intended that after handling
Water quality meet electrolytic manganese production requirement, while slag containing manganese returns to production and application.
The composition of the present invention：A kind of electrolytic manganese production Manganese in Waste Water recovery and waste water, the technique of waste gas integrated treatment, first locate
Manage chromate waste water and polishing waste water, it is characterised in that：Reducing agent is added in chromate waste water, by Cr6+It is reduced to Cr3+, add
Hydroxide adjusts pH, generates chromium hydroxide precipitation, and slag is stacked into Special slag field after precipitation separates, and filtrate enters to be given up containing manganese
Water；
Polish wastewater treatment：Hydroxide is added in waste water is polished and adjusts pH value to neutrality, vulcanizing agent is added and vulcanize and sink
Form sediment and react, produce sulfide precipitation, slag is stacked into Special slag field after precipitation separates, and filtrate enters Mn-bearing waste water；
Manganese recycles：Hydroxide is first added in waste water to collecting, adjusts pH to 7 ~ 8, it is rear to add carbonate deposition wherein Mn2 +, manganese carbonate is generated, manganous carbonate slag enters production system reuse after precipitation separation, and extraction raffinate carries out sulfate radical precipitation process；
Sulfate radical processing：Calcium hydroxide is added in above-mentioned extraction raffinate, sulfate radical precipitation reaction is carried out, treats residual sulfuric acid in solution
When root is less than 1g/L, separation of solid and liquid, liquid processed is passed through into solution caused by acid mist, solution ph is down to neutrality, solid-liquid solid
Produced for electrolytic manganese, filtrate returns to production head-tank and recycled.
It is industrial ferrous sulfate that reducing agent is added in chromate waste water processing, and addition is 1.5 times of chemical reaction amount, is stirred
Reaction time is 30 ~ 60 minutes, and additions hydroxide be industrial sodium hydroxide, regulation pH value for 10, the precipitation reaction time for 30 ~
60 minutes, precipitation separate mode was press filtration；
The hydroxide added in polishing wastewater treatment is industrial sodium hydroxide, and addition vulcanizing agent is DMDS for amino first
Sour sodium, is commonly called as：SDD, addition 0.5kg/m3, precipitation reaction time are 30 ~ 60 minutes, and solid-liquid separation method is press filtration；
It is industrial sodium hydroxide to add hydroxide in manganese recycling, and addition carbonate is agricultural ammonium bicarbonate, and addition is
1.5 times of chemical reaction amount, 2 ~ 3 hours precipitation reaction time, precipitation separate mode are press filtration after perpendicular stream precipitation；
Wherein calcium hydroxide be technical grade in sulfate radical precipitation, and addition is 1.5 times of chemical reaction amount, and the precipitation reaction time is
4 ~ 6 hours, precipitation separate mode was passed through acid mist gas and produced for liquid plant chemical combination, intake is to establish pressurization filter mode
100m3/ h, aeration time 0.5 ~ 1.0 hour, precipitation separate mode are ageing.
The advantages of compared with traditional electrolyte manganese waste water treatment process：
1st, be segmented in processing procedure, by chromate waste water and polishing waste water handled respectively, first processing containing heavy metal from
The waste water of son, so as to reduce the content of beary metal in manganous carbonate slag, be advantageous to manganous carbonate slag recycling；
2nd, electrolytic manganese production process is mainly rinsing workshop section with water, wastewater treatment increase sulfate radical handling process, reduces
SO4 2-Content, sulfate radical is set to be down to 2g/L or so from original more than 10g/L, greatly reduce sulfate radical in electrolysis flushing water
Influence to manganese piece sulfur-bearing；
3rd, present treatment technology key point：Because the pH value of water after processing sulfate radical is higher, it is impossible to be used in production, pH value need to be adjusted into
Property, by conventional process mode adjusted back with sulfuric acid, with sulfuric acid readjustment sulfate radical content increase, we are used instead in precipitated sulfur acid group
In waste water afterwards, be passed through Zhi Ye workshop sections caused by acid mist be aerated, replace sulfuric acid to adjust pH technique with this, obtain following
Both sides imitates state：First, cost is reduced（Without using sulfuric acid）, sulfate concentration in water is kept relatively low, do not influence product sulfur-bearing；
2nd, caused waste gas in production process has most importantly effectively been handled and has been given up using caused by the exhaust-gas treatment production process
Water, both remove processing water from and adjust pH sulfuric acid, eliminate expense caused by processing waste gas again, reduction water, gas pollution are effective to ensure
The zero-emission of water, gas, electrolytic manganese production is set to be preferably minimized pollution caused by environment.
Brief description of the drawings
Fig. 1 is sewage treatment technology process figure.
Embodiment
Embodiment 1：Chromate waste water 30m3, wherein Cr6+Content is 36mg/L, adds reducing agent ferrous sulfate thereto
52kg, stirring reaction 30min, detects Cr afterwards6+For 0.13mg/L, addition sodium hydroxide regulation pH value to 10, stirring reaction
30min, after carry out precipitation separation, chromium slag enters Special slag field, and extraction raffinate is mixed into Mn-bearing waste water；
Polish waste water 5m3, wherein：Cr3+48.63mg/L Ni2+28.68mg/L Fe2+136.25mg/L, Cu2+ 18.45mg/
L, pH is adjusted to neutrality with sodium hydroxide, vulcanizing agent SDD 2.5kg, stirring reaction 1h is added, carries out precipitation separation, slag enters special
With slag field, extraction raffinate is mixed into Mn-bearing waste water；
Comprehensive wastewater 100m3, wherein being 1800mg/L containing manganese, precipitating reagent carbon ammonium 700kg, stirring reaction 2.5h are added, Mn is surveyed and contains
Measure as 485mg/L, carry out precipitation separation, precipitation returns to production and application, and extraction raffinate enters to be handled in next step；
Above-mentioned processed waste water 95m3, survey SO4 2-Content 12g/L, add precipitating reagent lime 1300kg（Lime is prepared before use
Breast）, stirring reaction 4h, survey SO4 2-Content 1.2g/L, reuse requirement can be met, will after precipitation separation, survey filtrate pH value be 13 ~
14, acid mist caused by liquid process processed, while stirring reaction 50min are passed through into filtrate, surveys each composition of water sample such as following table：
Embodiment 2：Chromate waste water 30m3, wherein Cr6+Content is 55mg/L, adds reducing agent ferrous sulfate 80kg thereto, stirs
Reaction 30min is mixed, detects Cr afterwards6+For 0.09mg/L, add sodium hydroxide and adjust pH value to 10, stirring reaction 30min, it is rear to carry out
Precipitation separation, chromium slag enter Special slag field, and extraction raffinate is mixed into Mn-bearing waste water；
Polish waste water 5m3, wherein：Cr3+69.23mg/L Ni2+36.68mg/L Fe2+200.25mg/L, Cu2+ 10.45mg/
L, pH is adjusted to neutrality with sodium hydroxide, vulcanizing agent SDD 2.5kg, stirring reaction 1h is added, carries out precipitation separation, slag enters special
With slag field, extraction raffinate is mixed into Mn-bearing waste water；
Comprehensive wastewater 100m3, wherein being 2150mg/L containing manganese, precipitating reagent carbon ammonium 840kg, stirring reaction 2.8h are added, Mn is surveyed and contains
Measure as 360mg/L, carry out precipitation separation, precipitation returns to production and application, and extraction raffinate enters to be handled in next step；
Above-mentioned processed waste water 95m3, survey SO4 2-Content 13.5g/L, add precipitating reagent lime 1450kg（Lime is prepared before use
Breast）, stirring reaction 4h, survey SO4 2-Content 1.35g/L, reuse requirement can be met, will after precipitation separation, survey filtrate pH value be 13 ~
14, acid mist caused by liquid process processed, while stirring reaction 60min are passed through into filtrate, surveys each composition of water sample such as following table：
The above described is only a preferred embodiment of the present invention, any formal limitation, Ren Hewei not are made to the present invention
Disengaging technical solution of the present invention content, any simple modification made according to technical spirit of the invention to above example, etc.
With change and modification, in the range of still falling within technical solution of the present invention.
Claims (1)
1. a kind of electrolytic manganese production Manganese in Waste Water recovery and waste water, the technique of waste gas integrated treatment, first processing waste water containing chrome and throwing
Light waste water, it is characterised in that：Reducing agent is added in chromate waste water, by Cr6+It is reduced to Cr3+, add hydroxide regulation
PH, chromium hydroxide precipitation is generated, slag is stacked into Special slag field after precipitation separates, and filtrate enters Mn-bearing waste water；
Polish wastewater treatment：Hydroxide is added in waste water is polished and adjusts pH value to neutrality, vulcanizing agent is added and vulcanize and sink
Form sediment and react, produce sulfide precipitation, slag is stacked into Special slag field after precipitation separates, and filtrate enters Mn-bearing waste water；
Manganese recycles：Hydroxide is first added in waste water to collecting, adjusts pH to 7 ~ 8, it is rear to add carbonate deposition wherein Mn2 +, manganese carbonate is generated, manganous carbonate slag enters production system reuse after precipitation separation, and extraction raffinate carries out sulfate radical precipitation process；
Sulfate radical processing：Calcium hydroxide is added in above-mentioned extraction raffinate, sulfate radical precipitation reaction is carried out, treats residual sulfuric acid in solution
When root is less than 1g/L, separation of solid and liquid, liquid processed is passed through into solution caused by acid mist, solution ph is down to neutrality, solid-liquid solid
Produced for electrolytic manganese, filtrate returns to production head-tank and recycled；
It is industrial ferrous sulfate that reducing agent is added in chromate waste water processing, and addition is 1.5 times of chemical reaction amount, stirring reaction
Time is 30 ~ 60 minutes, and addition hydroxide is industrial sodium hydroxide, and regulation pH value is 10, and the precipitation reaction time is 30 ~ 60 points
Clock, precipitation separate mode are press filtration；
The hydroxide added in polishing wastewater treatment is industrial sodium hydroxide, and addition vulcanizing agent is DMDS for amino first
Sour sodium, is commonly called as：SDD, addition 0.5kg/m3, precipitation reaction time are 30 ~ 60 minutes, and solid-liquid separation method is press filtration；
It is industrial sodium hydroxide to add hydroxide in manganese recycling, and addition carbonate is agricultural ammonium bicarbonate, and addition is
1.5 times of chemical reaction amount, 2 ~ 3 hours precipitation reaction time, precipitation separate mode are press filtration after perpendicular stream precipitation；
Wherein calcium hydroxide be technical grade in sulfate radical precipitation, and addition is 1.5 times of chemical reaction amount, and the precipitation reaction time is
4 ~ 6 hours, precipitation separate mode was passed through acid mist gas and produced for liquid plant chemical combination, intake is to establish pressurization filter mode
100m3/ h, aeration time 0.5 ~ 1.0 hour, precipitation separate mode are ageing.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710995786.9A CN107522324B (en) | 2017-10-23 | 2017-10-23 | Process for recovering manganese in electrolytic manganese production wastewater and comprehensively treating wastewater and waste gas |
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| CN201710995786.9A CN107522324B (en) | 2017-10-23 | 2017-10-23 | Process for recovering manganese in electrolytic manganese production wastewater and comprehensively treating wastewater and waste gas |
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| CN107522324B CN107522324B (en) | 2020-10-13 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114212763A (en) * | 2021-12-17 | 2022-03-22 | 南方锰业集团有限责任公司大新锰矿分公司 | Resource utilization method of cathode plate polishing waste liquid for electrolytic manganese metal |
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|---|---|---|---|---|
| CN101691633A (en) * | 2009-10-12 | 2010-04-07 | 湖南广义科技有限公司 | Method for innocent treatment and comprehensive utilization of manganese slag |
| CN102139182A (en) * | 2011-01-21 | 2011-08-03 | 重庆武陵锰业有限公司 | Acid mist purifying method in electrolytic manganese leaching process |
| CN102358645A (en) * | 2011-08-05 | 2012-02-22 | 金瑞新材料科技股份有限公司贵州分公司 | Fully-closed circulation treatment method for water used by electrolytic manganese metal production |
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2017
- 2017-10-23 CN CN201710995786.9A patent/CN107522324B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101691633A (en) * | 2009-10-12 | 2010-04-07 | 湖南广义科技有限公司 | Method for innocent treatment and comprehensive utilization of manganese slag |
| CN102139182A (en) * | 2011-01-21 | 2011-08-03 | 重庆武陵锰业有限公司 | Acid mist purifying method in electrolytic manganese leaching process |
| CN102358645A (en) * | 2011-08-05 | 2012-02-22 | 金瑞新材料科技股份有限公司贵州分公司 | Fully-closed circulation treatment method for water used by electrolytic manganese metal production |
Non-Patent Citations (1)
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| 国家环境保护总局: "《中国环境保护标准全书》", 1 August 2007 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114212763A (en) * | 2021-12-17 | 2022-03-22 | 南方锰业集团有限责任公司大新锰矿分公司 | Resource utilization method of cathode plate polishing waste liquid for electrolytic manganese metal |
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